CN103842524A - Systems and methods for acid recycle - Google Patents
Systems and methods for acid recycle Download PDFInfo
- Publication number
- CN103842524A CN103842524A CN201280033775.8A CN201280033775A CN103842524A CN 103842524 A CN103842524 A CN 103842524A CN 201280033775 A CN201280033775 A CN 201280033775A CN 103842524 A CN103842524 A CN 103842524A
- Authority
- CN
- China
- Prior art keywords
- biomass
- approximately
- temperature
- acid
- rising
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C13—SUGAR INDUSTRY
- C13K—SACCHARIDES OBTAINED FROM NATURAL SOURCES OR BY HYDROLYSIS OF NATURALLY OCCURRING DISACCHARIDES, OLIGOSACCHARIDES OR POLYSACCHARIDES
- C13K13/00—Sugars not otherwise provided for in this class
- C13K13/002—Xylose
-
- C—CHEMISTRY; METALLURGY
- C13—SUGAR INDUSTRY
- C13K—SACCHARIDES OBTAINED FROM NATURAL SOURCES OR BY HYDROLYSIS OF NATURALLY OCCURRING DISACCHARIDES, OLIGOSACCHARIDES OR POLYSACCHARIDES
- C13K1/00—Glucose; Glucose-containing syrups
- C13K1/02—Glucose; Glucose-containing syrups obtained by saccharification of cellulosic materials
-
- C—CHEMISTRY; METALLURGY
- C13—SUGAR INDUSTRY
- C13K—SACCHARIDES OBTAINED FROM NATURAL SOURCES OR BY HYDROLYSIS OF NATURALLY OCCURRING DISACCHARIDES, OLIGOSACCHARIDES OR POLYSACCHARIDES
- C13K13/00—Sugars not otherwise provided for in this class
- C13K13/007—Separation of sugars provided for in subclass C13K
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P2201/00—Pretreatment of cellulosic or lignocellulosic material for subsequent enzymatic treatment or hydrolysis
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P2203/00—Fermentation products obtained from optionally pretreated or hydrolyzed cellulosic or lignocellulosic material as the carbon source
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- General Health & Medical Sciences (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
- Processing Of Solid Wastes (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
Methods and systems for pretreating lignocellulosic biomass are disclosed. An acid solution between 1% to 1.6% sulfuric acid is applied to the biomass. The biomass is subjected to an elevated temperature to cause the production of xylose, glucose, and furfural. Adjustments to temperature, acid concentration, and time can generate at least 80% or 90% of theoretical xylose, 45% or 50% of the theoretical glucose, and less than 4000 ppm of furfural in the xylose liquor. A portion of the resulting xylose liquor may be separated from the glucan solids. The xylose liquor, still highly acidic, can be recycled to reduce subsequent acid loading requirements. Makeup acid solution is added to the xylose liquor and subsequent biomass to ensure a proper solids to liquids ratio. The biomass is again treated to higher temperatures to yield sugars. The process may be repeated for each subsequent cycle.
Description
The cross reference of related application
The application requires on July 7th, 2011 to submit to, and title is the rights and interests of the U.S. Provisional Application series number 61/505,389 of " SYSTEMS AND METHODS FOR ACID RECYCLE ", and the full content of this application is incorporated herein by reference at this.
Technical field
The present invention relates to by sour recovery system and method in the xylose solution of cellulosic material production ethanol.The present invention also relates to for biomass are being provided to hydrolysis system, the system and method that is beneficial to High-efficient Production ethanol to preprocessing biomass before fermentation system is then provided.
Background technology
(for example can use raw grains material (for example corn, Chinese sorghum/chinese sorghum, barley, wheat, soybean etc.), carbohydrate, sugarcane, sugar beet etc.) and biomass cellulose raw materials such as (, timber or other vegetable material) such as switchgrass, corn cob and stalks produce ethanol.
Biomass comprise can be suitable for the directly vegetable material as fuel/energy, or can be used as the vegetable material that for example, is processed into another kind of biological product (biological example fuel, such as cellulosic ethanol) at biological refinery (logical ethanol plant) raw material.Biomass can comprise, for example, during harvesting corn grain and/or afterwards for example, fiber, switchgrass, farm or agriculture residue, wood chip or other Wood waste on the corn cob of gained and stalk (stem stalk and leaf), corn grain, and other vegetable material.In order to utilize or processing biological, gather from field by its harvesting, be then transported to the place of its utilization or processing.
Using biomass, example as noted above cellulosic material is produced in the biological refinery of ethanol, and ethanol is for example, to produce with ligno-cellulosic materials (, Mierocrystalline cellulose and/or hemicellulose).For example prepare biomass, to obtain the carbohydrate (, the wood sugar in glucose and hemicellulose in Mierocrystalline cellulose) in cellulose materials, and be fermented into the tunning that comprises ethanol (and other composition).Subsequently this tunning is sent into Distallation systm, by distillation and dewatering and recovery ethanol.Other biological product, for example xylogen and organic acid, also can be used as by-product recovery.How more effectively to prepare and to process the form and type or the composition that are (except other side) biomass for the production of the determinative of the biomass of ethanol.
The pre-treatment of biological material is an expensive step for the preparation of the ligno-cellulosic materials of fermentation, and in order to be sugar by cellulose degradation, this step need to suppress PH.Conventionally, utilize heavy dose of acid to make the pH value of biomass reach the required level of effectively C5 sugar being separated from C6 solid.Being very huge for the required sour volume of plant-scale cellulosic ethanol plant, is very expensive for buying and preserving.Further, subsequently at downstream process, for example must be these a large amount of acid neutralizations before fermentation.Neutralization also can be followed significant cost, and may cause unnecessary mineral substance, and these mineral substance may be accumulated in down-stream system.
Summary of the invention
The disclosed aspect of the application relates to the system and method for preprocessing lignocellulose biomass.Pretreated biomass offer fermentation system, or saccharification system follows by fermentation system, for the production of leavened prod.In certain embodiments, these biomass can comprise ground corn cob, grain stem, or the mixture of ground corn cob and grain stem.In certain embodiments, this leavened prod can be ethanol or other biofuel.
In certain embodiments, a kind of method comprises acidic solution is applied to first part's biomass.In certain embodiments, this acidic solution can comprise approximately 1% to approximately 1.6% sulfuric acid.In order to produce wood sugar in xylose solution He in dextran solid, can make these biomass process for some time at elevated temperatures.In certain embodiments, temperature is maintained at about 120oC between approximately 150 oC, and the time is approximately 10 minutes to approximately 120 minutes.
The temperature raising can cause the generation of wood sugar, glucose and furfural.On the one hand, the theoretical wood sugar of generation at least about 80%.In certain embodiments, temperature, acid concentration, and/or the time can optimization (for example, changing), to produce the theoretical wood sugar at least about 90%.Similarly, can pass through improved conditions (for example temperature, acid concentration, and/or time) and guarantee to produce about 45% or the theoretical glucose of more (for example about 50%).Because more violent pre-treatment can produce higher sugar level, in certain embodiments, can control severe degree, thereby produce the sugar of wanting, and can not cause that the furfural that is greater than about 4000ppm or about 3000ppm appears in xylose solution.
After the Temperature Treatment raising, the xylose solution that at least a portion produces may be separated from dextran solid.In certain embodiments, dextran solid can offer saccharification system.In some implementations, be recoverable to about 70% xylose solution.In other embodiments, be recoverable to about 75% xylose solution.
This xylose solution remains highly acidic, can reclaim to reduce sour carriage requirement below.Xylose solution and generate subsequent material added supplementary acid solution to help guaranteeing to meet suitable solid to liquor ratio in the past.Thereby biomass can produce sugar with higher Temperature Treatment again.According to one side, for follow-up each circulation, this process can repeat.
Accompanying drawing explanation
To, by example, by reference to the accompanying drawings, some embodiment be described below, more clearly to illustrate disclosed aspect.
Figure 1A is the skeleton view that comprises the biological refinery of alcohol production equipment according to some embodiment.
Figure 1B is another skeleton view that comprises the biological refinery of alcohol production equipment according to some embodiment.
Fig. 2 is the process flow sheet of having shown preparation biomass according to some embodiment.
Fig. 3 A and 3B are according to some embodiment, have shown the process flow sheet of the example of the ethanol production process from biomass to ethanol.
Fig. 4 is the preparation for lignocellulose biomass according to some embodiment, pre-treatment and the device separating.
Fig. 5 is for reclaiming the exemplary plot of theoretical xylose concentration of xylose solution according to some embodiment.
Fig. 6 is for reclaiming the exemplary plot of theoretical acetic acid concentration of xylose solution according to some embodiment.
Fig. 7-10th, according to some embodiment, for various processing condition, the exemplary plot of the xylose concentration in preprocessing biomass and the relation of recovered frequency.
Figure 11-13rd, according to some embodiment, for various processing condition, the exemplary plot of the glucose concn in preprocessing biomass and the relation of recovered frequency.
Figure 14-16th, according to some embodiment, for various processing condition, the exemplary plot of the acetic acid concentration in preprocessing biomass and the relation of recovered frequency.
Figure 17-19th, according to some embodiment, for various processing condition, the exemplary plot figure of the furfural content in preprocessing biomass and the relation of recovered frequency.
Table 1A and 1B have enumerated according to one exemplary embodiment and exemplary embodiments, the composition of the biomass that contain the lignocellulosic plants material that is derived from milpa.
Table 2A and 2B have enumerated according to one exemplary embodiment and exemplary embodiments, the composition of the liquid component of pretreated biomass.
Table 3A and 3B have enumerated according to one exemplary embodiment and exemplary embodiments, the composition of the solids component of pretreated biomass.
Table 4 has been enumerated according to one exemplary embodiment and exemplary embodiments, for theoretical acid and the water of various recovery numbers.
Table 5 has been enumerated according to one exemplary embodiment and exemplary embodiments, the experiment condition of the example that number acid reclaims.
Table 6 has been enumerated according to one exemplary embodiment and exemplary embodiments, the wood sugar under the recovering condition of table 5, the result of glucose and furfural.
Embodiment
Below in conjunction with the some related embodiment shown in accompanying drawing, describe various aspect of the present invention in detail.Hereinafter list many details, being intended to provides complete understanding for the embodiment of one or more aspects.But for this area related personnel, these embodiment obviously can also implement in the situation that lacking some of them or whole detail.In some other embodiment, well-known processing step and/or structure all do not add detailed description, are intended to avoid increasing unnecessary understanding difficulty to each aspect of the present invention.
Each side disclosed herein relates to the system and method for the acid recovery in the cellulosic acid pre-treatment for the production of ethanol.This system and method availability valency is than high method, for reduce the acid of cellulosic ethanol refinery and the consumption of water in keeping xylose and glucose output.For example, provide in alcohol production for biomass pre-treatment and reduce the system and method for sour demand.Also provide to reduce between the biomass pre-treatment period of cellulosic ethanol refinery and use supplementary acid, the system and method for the necessity of water and neutralization reagent.
Referring to Figure 1A, show the biological refinery 100 of example, it comprises the alcohol production equipment for produce ethanol with biomass.Thereby comprising to send to and prepare biomass, the biological refinery 100 of this example provides to the region of alcohol production equipment.This cellulosic ethanol production equipment comprises Preparation equipment 102, pre-processing device 104 and treatment facility 106, and this treatment facility 106 can be the processing artifact matter that is adapted at being fermented in fermentation system tunning by biomass processes.This cellulosic ethanol production equipment comprises Distallation systm 108, and this system can be distilled and dewater tunning and be generated ethanol.Waste treatment system 110(comprises anaerobic digester and producer as shown in Figure 1A) be also included in biological refinery 100.In other optional embodiment, this waste treatment system can comprise for the treatment of, process and get back the miscellaneous equipment of the composition in cellulosic ethanol production technique, for example solid/waste fuel boiler, anaerobic digester, aerobic digester or other biochemistry or chemical reactor.
As shown in Figure 1B, in an exemplary embodiment, biological refinery 112 can comprise with alcohol production equipment 116(based on corn produce ethanol from the endosperm part starch contained therein of corn grain) the cellulosic ethanol production equipment 114(of Alignment produces ethanol from ligno-cellulosic materials and the composition of milpa).As shown in Figure 1B, overlap alcohol production equipment by Alignment two, can share some factory system, for example, for the dehydration of ethanol, store, the system of sex change and transportation, energy/fuel is to the generation systems of energy, factory management and Controlling System, and other system.The zein fiber (composition of corn grain) for example, obtaining in the time of the corn grain for the preparation of abrasive dust (, fractionation) in the alcohol production equipment based on corn is supplied to cellulosic ethanol production equipment as raw material.The fuel obtaining from cellulosic ethanol production equipment or the energy, for example methane or xylogen, can be used for to equipment or one of them energy supply of two cover Alignments.According to other optional embodiment, biological refinery (for example, cellulosic ethanol production equipment) can with the facilities and equipment Alignment of other type, for example power station, waste reduction and disposal equipment, logging headquarter, paper mill or processing of farm products factory.
Referring to Fig. 2, show for the preparation of the system 200 of biomass of delivering to biological refinery.This biomass preparation system can comprise device, cleaning equipment (for example, removing impurity), the grinding plant (for example abrasive dust, compression or multiviscosisty) for receiving/unload biomass and send into the handling equipment of factory process.According to one exemplary embodiment, the biomass of corn cob and stalk form can be delivered to biological refinery and store 202 (for example, bundled, in heaps or become case to store, etc.) and management, use for equipment.In an one exemplary embodiment, these biomass can contain corn cob (by weight) and maize straw and other material at least about 20% to 30%.According to other one exemplary embodiment, the preparation system 204 of biological refinery can for example, for the preparation of polytype biomass (, vegetable material), and ethanol and other biological product are processed and be processed into these biomass in factory.
Referring to Fig. 3 A and 3B, the optional embodiment 300a of cellulosic ethanol production equipment and the schematic diagram of 300b are shown.According to some embodiment, in preparation system, prepare and clean the biomass that comprise from the vegetable material of milpa.After preparation, these biomass and water are mixed into slurry, and carry out pre-treatment in pretreatment system 302.In pretreatment system 302, biomass be decomposed (for example, by hydrolysis), so that separate 304 be liquid component (for example, the liquid stream that contains C5 carbohydrate, is called pentaglucose liquid stream) and solids component (for example, containing the cellulosic liquid stream that can be used for manufacturing C6 carbohydrate).Thereby promote C5 to separate in order to reduce biomass PH, pre-treatment can comprise adds acid.According to some aspects, in order to reduce the acid of pretreatment system and the level of water of being supplied to, C5 liquid stream reclaims the treatment stage of also can be from C5, as shown in the figure.The object lesson of recovering condition, volume and processing condition relevant to specific embodiment is below provided more in detail.But, also can utilize other recovering condition, volume and processing condition.
Can in pentose clean system 306, process the liquid component (C5 liquid stream or pentaglucose liquid stream) that contains C5 carbohydrate.From this pentose clean system 306, the recovery liquid stream of xylose solution can turn back to above-mentioned pretreatment system 302.
The pretreated solids component that contains C6 carbohydrate also can produce carbohydrate by enzymically hydrolyse in solids management system 308.According to embodiment, can be hydrolyzed (for example enzymically hydrolyse) obtains the C6 carbohydrate in Mierocrystalline cellulose; Also the xylogen that can attempt removing in C6 liquid stream by processing can not fermented ingredient (or removing such composition: for example residual acid maybe may have inhibiting acids to effective fermentation) with other.Can improve enzymically hydrolyse efficiency by adding reagent.This reagent can comprise anaerobism membrane digestion pond sewage, clarification stillage (clarified thin stillage), wet cake, unfiltered stillage (whole stillage), the protein source that other is feasible, or its mixture.The processing details of C6 solid will be described below.
According to the embodiment shown in Fig. 3 A, pentaglucose liquid stream after treatment can ferment in pentose fermentation system 310, and its tunning can be supplied to pentose Distallation systm 312 to reclaim ethanol.Similarly, do not comprise the solids component after treatment of a large amount of C6 carbohydrates, can be supplied to zymohexose system 314, and leavened prod can be supplied to hexose Distallation systm 316 to reclaim ethanol.Can in lignin separation system 318, process from the stillage distilling to produce liquid component and solid wet cake.In certain embodiments, wet cake is supplied to anaerobism mould material bio-reactor (Anaerobic Membrane Bioreactor, AnMBR) 320 further to process.
In the alternate embodiment of Fig. 3 B, the pentaglucose liquid after treatment of gained flows and solids component after treatment can mix (for example, becoming slurry) after processing and co-fermentation in fermentation system 322.Can be supplied to composite distillation system 324 and therefrom reclaim ethanol from the tunning of fermentation system 322.According to an embodiment or more embodiment, in fermentation system, can utilize suitable fermenting organism (producing and ethanol bacterium ethanologen).Selecting of producing and ethanol bacterium ethanologen can be based on multiple consideration, for example main carbohydrate type in slurry.The ethanol of producing with C5 liquid stream and C6 liquid stream, its dehydration and/or modification can separate or jointly carry out.The same with previously described embodiment, can in lignin separation system 326, process from the stillage distilling to produce liquid component and solid wet cake.In certain embodiments, wet cake is then supplied to anaerobism mould material bio-reactor (AnMBR) 328 further to process.
During processing C5 and/or C6 liquid stream, for example can process each composition, to reclaim by product, organic acid and xylogen.Process and flow the biomass production ethanol of both or one of them from C5 liquid stream and C6 liquid during (or distillation), can by the one-tenth divisional processing removing and be processed into biological product or fuel (for example, for the xylogen of solid fuel fired boiler, or by the residue such as acids and xylogen such as in anaerobic digester/the remove methane that thing processing obtains), or be used and recycle through reclaiming.
According to embodiment, these biomass comprise the vegetable material from milpa, for example corn cob, milpa crust, corn leaf and Maize Stem (for example, at least half or 3/4ths part of Maize Stem upper end).The composition (for example, Mierocrystalline cellulose, hemicellulose and xylogen) of this vegetable material approximately (for example, at least passes through the preparation first of biomass, comprises and remove all impurity) as shown in table 1A and 1B.According to embodiment, this vegetable material comprises corn cob, shell/leaf and stem.For example, this vegetable material can contain (by weight) from milpa up to 100% cob, up to shell/leaf of 100%, approximately 50% cob and approximately 50% shell/leaf, approximately 30% cob and approximately 50% shell/leaf and approximately 20% stem, or any in multiple other array mode of cob, shell/leaf and stem.As show as shown in 1A.According to another alternate embodiment, this lignocellulosic plants material can comprise the fiber (for example, mixing with other vegetable material) from corn grain.Table 1B provides and has been considered to representative and comprises the scope from the typical and expection of the composition of the biomass of the ligno-cellulosic materials of milpa.According to one exemplary embodiment, the lignocellulosic plants material in should (from milpa) biomass can comprise (by weight) approximately 30% to approximately 55% Mierocrystalline cellulose, approximately 20% to approximately 50% hemicellulose and approximately 10% to approximately 25% xylogen.According to specific embodiment, lignocellulosic plants material (for example, the cob of milpa, shell/leaf and stem portion) in these biomass can comprise (by weight) approximately 35% to approximately 45% Mierocrystalline cellulose, approximately 24% to approximately 42% hemicellulose and approximately 12% to approximately 20% xylogen.According to specific embodiment, the pre-treatment of these biomass can produce and comprise that (by weight) is not less than the liquid component of approximately 1.0% wood sugar and comprises that (by weight) is not less than the approximately 45% Mierocrystalline cellulose solids component of (can be used for producing glucose).
Fig. 4 has shown according to one exemplary embodiment, for preparation, the pre-treatment of lignocellulose biomass and the device 400 separating.As shown in the figure, at shredder 402(for example, shredder or other suitable equipment or pulverizing mill) prepare biomass.To reactor 404(or a group reaction device) supply the biomass that prepare, the acid of predetermined concentration (or PH) and/or water and other operational condition, carry out pre-treatment to the biomass that prepare.Pretreated biomass can be separated into liquid component (C5 liquid stream at whizzer 406, mainly comprise liquid, and some solids) and solids component (C6 liquid stream, comprises liquid and solid, for example xylogen and Mierocrystalline cellulose, can be further processed and generate glucose it).
According to embodiment, in pretreatment system, acid can be applied to the biomass that prepare, to promote biomass decomposition, thereby be separated into liquid (pentaglucose liquid stream) composition (can therefrom reclaim the C5 liquid stream of fermentable C5 carbohydrate) and solids component (can therefrom obtain the C6 liquid stream of fermentable C6 carbohydrate).According to embodiment, can be in definite operational condition (for example, acid concentration, pH, temperature, time, pressure, solids loading, flow velocity, process water or steam supply amount, etc.) under this acid is applied to the biomass in reactor, and in reactor, these biomass are carried out to stirring/mixing, to promote the decomposition of biomass.According to one exemplary embodiment, can be by acid, for example sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, acetic acid etc. (or preparation/mixture of acid) are applied to this biomass with the recovery liquid stream of xylose solution.The recovery liquid stream of xylose solution comprises enzyme, and acid and water can be reduced in pretreatment system and add other acid and the requirement of water.Can realize the maximization of sugared burst size and minimizing of inhibitor generation by careful control wood sugar recovery volume and processing condition.Table 4 provides, and acid used and the theoretical value of water depend on the xylose solution volume of the recovery during pre-treatment step.In addition, provide the economic data about new sour cost.Calculate the use of the acid/water of 10 pre-treatment circulations of the recovery liquid stream that uses various quantity.Calculating is based on 1000kg cob, and 14.3% solids loading uses 1% H
2sO
4in.Reclaiming a large amount of xylose solutions in upper once pre-treatment causes the per-cent of the quantity of acid used in follow-up pre-treatment and water to decline larger.Also find, by reclaiming liquid stream, the xylose concentration of xylose solution and the flow quantity of recovery increase pro rata.The efficiency of the maximum value of recuperable liquid stream based on solid-liquid separation and the flow quantity of obtaining from liquid stream operation.As shown in the figure, increase with the volume of the xylose solution reclaiming, the usage quantity of water and sour increasing amount obviously reduce.In certain embodiments, water and sour reduction can be up to 70%.
According to embodiment, Fig. 5 has shown various recovery volumes, the exemplary plot 500 of the theoretical concentration 502 of wood sugar in the xylose solution that cycle number is 504.The calculating of the theoretical xylose concentration of the xylose solution reclaiming is the 100% wood sugar output (every 100 g cob 32g wood sugars) of carrying out pre-treatment and producing with cob based on the solid to 14.3%.502 have 32g wood sugar by hypothesis in the solution from pretreated 700g, calculate xylose concentration, and causing concentration in first pre-treatment is 4.57%.Then, a certain amount of liquid stream is carrying a certain amount of wood sugar and can in upper once pre-treatment, reclaim, thereby can increase the wood sugar amount producing between 100g cob (32g wood sugar) pre-treatment period.In follow-up circulation, xylose concentration increases until xylose concentration level is fair with stable state value.The volume reclaiming is larger, turns back to wood sugar in pre-treatment more, and the xylose concentration therefore further increasing is away until saturated.For example, according to the theoretical value of Fig. 5, reclaim 70% xylose solution, after 20 circulations, final xylose concentration estimates to reach approximately 11.43% w/v.
Similarly, according on the one hand, Fig. 6 shown various recovery volumes, and the acetic acid 602(of the xylose solution in cycle number 604 is fermentation inhibitor in some concentration) exemplary plot 600 of theoretical concentration.Similar assumed condition used Fig. 5 is used for simulating acetic acid concentration.First circulation, in general, the acetic acid concentration of generation is about 6186ppm.In follow-up circulation, acetic acid concentration increases until acetic acid concentration level and steady state value maintain an equal level.The volume reclaiming is larger, turns back to acetic acid in pre-treatment more, and the acetic acid concentration therefore further increasing is away until saturated.For example, according to the theoretical value of Fig. 6, reclaim 70% xylose solution, after 16 circulations, final acetic acid concentration estimates to reach about 15457ppm.
According to specific embodiment, except the recovery liquid stream of xylose solution, sulfuric acid can be applied to pretreated biomass.According to specific embodiment, can for example, be about 100 to 180 degrees Celsius with about 0.8% to about 1.5% acid (, sulfuric acid) and about biomass solid of 12% to 25% in temperature and the biomass that prepare be carried out to the pre-treatment of about 5 to about 180 minutes.In replaceable embodiment, the xylose solution of setting volume is supplied with to biomass.Use concentrated acid, for example sulfuric acid adjusts to about 1.5 the PH of biomass.The use minimizing that wood sugar reclaims liquid stream makes PH reach the required total mineral acid of pre-treatment acceptable level.Pre-treatment can comprise steam explosion step, now biomass are heated to and under atmospheric pressure (for example, 100psi) (for example keep, hold-time) about 150 to about 165 degrees Celsius, pH value is about 1.4 to about 1.6, time is about 1 to about 15 minutes, and then pressure further discharges help decomposition of cellulose.As shown in Figure 4, after pre-treatment, pretreated biomass are separated into solids component (C6) and liquid pentaglucose liquid stream composition (C5).
This liquid pentaglucose liquid stream composition (C5 liquid stream) comprises water, for example, by the solvable carbohydrate for being fermented into ethanol (wood sugar, pectinose and glucose), sour and other solvable composition of reclaiming from hemicellulose.(table 2B is depicted as the typical case and the desired extent that are considered to comprise from the representative compositions of the biomass of the ligno-cellulosic materials of milpa.) according to one exemplary embodiment, this liquid component can comprise that about 5% for example, to about 7% solids component (suspension/residual solids, such as hemicellulose, Mierocrystalline cellulose and the xylogen of partial hydrolysis).According to specific embodiment, this liquid component comprises that at least about 2% to about 4% wood sugar (by weight).According to other one exemplary embodiment, this liquid component comprises the wood sugar (by weight) that is no less than about 1% to about 2%.Table 2A and 2B listed according to exemplary and representational embodiment, the composition of the liquid component of (from showing the biomass that prepare shown in 1A and 1B) pretreated biomass.Part C5 xylose solution body fluid flow can reclaim in above-mentioned pre-treatment.In certain embodiments, the xylose solution of all (or substantially all) can reclaim.In the disposable embodiment of xylose solution of all (or substantially all), the remaining xylose solution not reclaiming for example, was processed with alkali (sodium hydroxide, lime, or ammonium hydroxide) before being introduced in fermentation.In certain embodiments, can carry out other inhibitor to xylose solution and remove processing.
This solids component (C6 liquid stream) comprises water, acid and solid for example can generate sugar, such as glucose is to be fermented into the Mierocrystalline cellulose of ethanol, and xylogen.(table 3B provides typical case and the desired extent of the representative compositions of the biomass that are considered to the ligno-cellulosic materials that comprises milpa.) according to one exemplary embodiment, this solids component can comprise that about 10% to about 40% solid (by weight) (after separating).According to specific embodiment, this solids component can comprise that about 20% to about 30% solid (by weight).According to another embodiment, the solid in this solids component comprises the Mierocrystalline cellulose that is no less than about 30%, and this solids component can also comprise other soluble saccharide (for example, glucose and xylose).Table 3A and 3B listed according to exemplary and representational embodiment, the composition of the solids component of (since as shown the biomass that prepare as shown in 1A and 1B) pretreated biomass.
After C5 liquid component is separated from C6 solid, solid can further be processed in enzymic hydrolysis system.According to embodiment, after pre-treatment, solids component (C6) and enzyme, reagent is supplied to the container for enzymic hydrolysis (or saccharification) together with water.Enzyme for example can promote pretreated cellulose decomposition, for sugar (, glucose) thereby produce enzymic hydrolysis product.Follow this sugar that is rich in enzymic hydrolysis product and can be fermented into ethanol, or for any other downstream process.
In certain embodiments, can carry out a series of hydrolysis and fermentation (SHF) technique to C6 solid, wherein solid be carried out to enzymic hydrolysis (dextran transformation efficiency is at least 80%), then ferment.When using when two-step process, adopt SHF method, enzymic hydrolysis can be carrying out at the best pH of cellulose conversion saccharogenesis (or approaching as far as possible best pH) and temperature.For SHF, at about 50 ° of C, in about 5.5 pH and about 15% total solids slurry and cellulase, process solid.
Selectively, can carry out to C6 solid (or almost simultaneously) saccharification and fermentation (SSF) operation, wherein enzymeization hydrolysis and fermentation are carried out simultaneously simultaneously.According to one side, (or approaching simultaneously) execution saccharification and enzymeization can be in the temperature (being about 37oC) that is suitable for yeast generation ethanol simultaneously, and for cellulose enzymeization, this is optimal.
According to one exemplary embodiment, be supplied to solids component (C6) to promote enzymic hydrolysis the zymin that comprises the cellulolytic enzyme of energy, for example, polymer fiber element (for example polymerization dextran) becomes accessible monose (for example, monomer glucose) by the saccharification of enzyme effect.The example of these cellulases is from Franklinton, the Novozymes North America of North Carolina, the Cellic CTec (for example, NS22074) of Inc. company.Enzyme preparation amount or loading capacity (dosage) can change with operational condition.According to one exemplary embodiment, every gram of Mierocrystalline cellulose can add the zymoprotein of about 2 to about 12 milligrams.According to specific embodiment, every gram of Mierocrystalline cellulose can add the zymoprotein of about 3 to about 9 milligrams.
According to one exemplary embodiment, the temperature during processing solids component (C6) can be about 30 to about 60 degrees Celsius.According to embodiment, process temperature during solids component (C6) and can be about 45 to about 55 degrees Celsius, according to specific embodiment, the temperature during processing solids component (C6) can be about 49 to about 51 degrees Celsius.
According to one exemplary embodiment, the treatment time of solids component (C6) can be about 48 to about 144 hours.According to embodiment, the treatment time of solids component (C6) can be about 60 to about 120 hours, and according to specific embodiment, the treatment time of solids component (C6) can be about 72 to about 96 hours.
According to one exemplary embodiment, it can be about 5% to about 25% weight that the solids content of solids component (C6) is supplied to treatment system.According to embodiment, the solids content of solids component (C6) can be about 10% to about 20% weight, and according to specific embodiment, the solids content of solids component (C6) can be about 12% to about 17% weight.
According to one exemplary embodiment, the pH during processing solids component (C6) can be about 4.8 to about 6.2.According to embodiment, process pH during solids component (C6) and can be about 5.2 to about 5.8, according to specific embodiment, the pH during processing solids component (C6) can be about 5.4 to about 5.6.
At enzymic hydrolysis biomass (corn cob, crust, leaf and/or stem) during, use available cellulase and do not add rare stillage (thin stillage), clarify the scope of the glucose yield that rare stillage (clarified thin stillage) or anaerobism film reactor sewage reaches, concerning while (or almost simultaneously) saccharification and fermentation (SSF), can be approximately 35% to about 40% glucose theoretical yield (for example, calculate), and for being hydrolyzed in order and ferment (SHF), glucose yield theory that can be between about 55% to about 70% (for example, calculate).Depend on pretreatment process, glucose yield can change accurately.For example, as mentioned above, comprise steam explosion pre-treatment, the biomass of processing for SHF, can increase glucose conversion output.
As described herein, relate in one aspect to the method for preprocessing lignocellulose biomass.The method can comprise acidic solution is applied to first part's biomass, and makes first part's biomass remain on the temperature of rising, thereby obtains the approximately more than 80% wood sugar output of theoretical wood sugar output.In the time remaining on the temperature of rising, from first part's biomass, produce liquid xylose solution and dextran solid.The method can also comprise and from dextran solid, separates the liquid xylose solution of at least a portion, operative liquid xylose solution is applied to further part biomass, and supplementary acid solution is applied to further part biomass.Further, thus the method can comprise the temperature that makes further part biomass remain on rising can obtain the approximately more than 80% wood sugar output of theoretical wood sugar output.In the time remaining on the temperature of rising, from further part biomass, produce liquid xylose solution and dextran solid.The method can start repetition from liquid xylose solution to the further part biomass of separate part.In certain embodiments, the method can comprise release glucose.
In an embodiment, the temperature that remains on rising can comprise and maintains the temperature at about 120oC to about 150oC.In another embodiment, the temperature that remains on rising can comprise at least about 10 minutes of the temperature that remains on rising.In embodiment further, the temperature that remains on rising can comprise that the temperature that remains on rising is less than about 120 minutes.
In certain embodiments, application acid solution can comprise the acid solution that is applied as the sulfuric acid between about 1% to 1.6%.In certain embodiments, can keep the temperature of rising of first part's biomass and the temperature of the rising of further part biomass, until realize the theoretical wood sugar output that is greater than 90%.In other embodiments, can keep the temperature of rising of first part's biomass and the temperature of the rising of further part biomass, until realize the theoretical glucose yield that is greater than 45%.In certain embodiments, can keep the temperature of rising of first part's biomass and the temperature of the rising of further part biomass, until realize the theoretical glucose yield that is greater than 50%.
On the one hand, liquid xylose solution comprises the furfural that is less than about 4000ppm.In some respects, liquid xylose solution comprises the furfural that is less than about 3000ppm.According to some aspects, operative liquid xylose solution is total xylose solution of 70%.According to other side, operative liquid xylose solution is total xylose solution of 75%.
Relate on the other hand the method for pre-treatment fermentation system to be supplied to the lignocellulose biomass of production tunning.The method can comprise xylose solution is applied to biomass, supplementary acid solution is applied to biomass, and makes biomass remain on the temperature of rising, thereby obtain the approximately more than 80% wood sugar output of theoretical wood sugar output.In the time remaining on the temperature of rising, can from biomass, produce liquid xylose solution and dextran solid.The method can also comprise and from dextran solid, separates at least a portion xylose solution.The method can repeat acid solution to be applied to biomass.
Embodiment
In the one exemplary embodiment of this system, carry out a series of limited examples, attempt evaluating the effect of the various volumes that are recycled and processing conditions.Test and test, to evaluate the relation of xylose concentration, glucose yield, acetic acid concentration and inhibitor level (such as furfural) and recovery volume, cycle number and processing conditions.Below experiment is intended to some embodiment of the system of illustrating and operating method, is not intended to limit the scope of each side disclosed herein.
Table 5 provides embodiment test conditions, comprises the general introduction of pretreatment temperature, cycle number, sulfuric acid concentration and timing.For all embodiment, utilize known HPLC(high performance liquid chromatography) analytical technology is measured sugar, furfural/5-hydroxy-methyl furfural (HMF), and acetic acid level.After saccharification step, measure glucose concentration.Further, regulate through pretreated fill-in, change with the humidity that adapts to geodyte quality sample.For each embodiment condition, will own (substantially all) pretreatment fluids stream and reclaim in next circulation (except the little experiment volume for analyzing).
For all embodiment, cob material is beaten and is pulverized and be stored in quonset hut formula (Quonset hut style) buildings, thus the environment keeping dry, and bottom line or be not exposed to sunlight and severe weather.From Fisher Scientific (from Waltham, MA) for
babcock Milk Testthe form of the reagent of SA174-4 91.6% acid obtains sulfuric acid.
Utilize ground cob to prepare 14.3% solid solution and containing the sour acid solution of sour normality that is useful on pretreatment condition, as shown in table 5.1 L Pa Er reactor loads the ground cob that dry weight is 100g.Water and sulfuric acid mix the acid concentration to realize ideal at liquid portion, count the water that biomass bring simultaneously in and then join the water in biomass starting material.Stir acid solution and cob so that all sample is moistening with spatula.Then this container is connected and is stirred under 450 rpm with Pa Er reactor upper end.By providing high pressure steam (250 to 300 psi) to container chuck, to heat.By the thermocouple monitoring temperature in thermopair outer tube.By adding container chuck to adjust temperature steam or cold water.As long as container contents reaches temperature required, reaction timing register just starts.After suitable time of vessel insulation, utilize water to make container cooling by container chuck.
After having reacted, remove Pa Er reactor and pre-treatment slurry is transferred to deadweight (tared) 1000 ml polypropylene centrifuge tubes.Then, by centrifugal 15 minutes separating slurries of 4500 rpm.Adopt oven for drying moisture operation to determine the moisture content of solid, be then used in enzymatic saccharification.By the xylose solution sample of 30g for sugar (wood sugar, glucose and pectinose), HMF, furfural, acetic acid, and total solids (dissolving with suspend) analysis.The residual content of liquid stream is as next pretreated recovering liquid.
Subsequently, water is diluted to 10% by solid.In 125 ml erlenmeyer flasks (Erlenmeyer flask), analyze with 70ml slurry.Utilize the water-soluble potassium hydroxide of 45% w/w or the water-soluble sulfuric acid of 10% v/v that the PH of the slurry in each flask is adjusted to 5.5.Enzyme carrying capacity is every g dextran 9 mg zymoproteins (glucan content of solid part is assumed to 35%).Flask is stirred at 150 rpm with 50 ° of C(in shaking bath) cultivate 72/96 hour.
Carry out removal process by the ground cob that loads dry weight 100 g in Pa Er reactor, pretreated recovering liquid before adding, utilizes dilute acid solutions, with the suitable acid concentration from table 5, reacting weight is adjusted to 700 g.Then (or almost comparably) implements preprocessing process to each recycling step comparably.This removal process repeats the number of times of specifying in experimental design.
In experiment, xylose concentration, glucose concn and acetic acid concentration under the each condition shown in analytical table 5.Collect xylose solution and inject HPLC bottle by 2 μ m syringes and filter.Then bottle is loaded on replacing dish, replacing dish is fixed on automatic sampler (from Milford, 717 Plus of the Waters company of MA or 2659 separation modules).By aliquot sample, (5 μ l) are injected into by automatic injector the reversed-phase column (from Hercules, the HPX-87H in the Bio-Rad laboratory of CA) that remains on 50oC.Using the sulfuric acid of 0.005M as moving phase (elutriant).HPLC system disposition RI-detector (from 2410 or 2414 modules of Waters from waters).Utilize Empower software (Waters) to identify with quantitative composition (sugar, organic acid, and ethanol).
Furfural and HMF concentration under each condition shown in his-and-hers watches 5 are analyzed.Water dilutes xylose solution in the water of ten times, and is infiltrated in HPLC bottle and filtered by 0.2 μ m nylon syringe, prepares sample.10 μ l aliquot samples are injected on the reversed-phase column of 40 ° of C by HPLC automatic injector (Dionex Ultimate 3000).Use the water by 90:5:5: acetonitrile: what methanol solution formed flows with the flow velocity phase elution samples of 1ml/min.Detect furfural and HMF by UV with 280 nm wavelength.Later stage wash-out compound is washed off post and is passed through by 50:10:40 water: acetonitrile: the post moving phase that methyl alcohol forms, with the flow velocity of 1ml/min, is washed off from pillar for 5 minutes.
The analytical results of the relation of wood sugar and recovered frequency has been shown in Fig. 7-10.Especially, Fig. 7 has shown that the exemplary plot 700(that different circulation 704 is processed sample at 120o C to the wood sugar output per-cent 702 of 120 minutes with various acid solutions describes in detail as table 5).Fig. 8 has shown that the exemplary plot 800(that different cycle number 804 is processed sample at 140o C to the wood sugar output per-cent 802 of 20 minutes with various acid solutions describes in detail as table 5).Fig. 9 has shown the exemplary plot 900 of the wood sugar output per-cent 902 of the sample of processing with different cycle number 904 in various time and temperature with 1% acid solution.Figure 10 has shown the exemplary plot 1000 of per-cent wood sugar (w/v) 1002 in pretreatment fluid stream and the relation of recovered frequency 1004.As shown in the figure, xylose concentration increases with recovered frequency, until reach Css.In this embodiment, maximum hammer butt candy output is realized with the pre-treatment that 1% acid solution carries out 10 minutes with 150oC temperature.
The analytical results of the relation of glucose and recovered frequency has been shown in Figure 11-13.Especially, the exemplary plot 1100(that Figure 11 has shown glucose yield per-cent 1102 and the relation of recovered frequency 1104 of with various acid solutions, sample being processed to 120 minutes at 120oC describes in detail as table 5).The exemplary plot 1200(that Figure 12 has shown glucose yield per-cent 1202 and the relation of recovered frequency 1204 of with various acid solutions, sample being processed to 20 minutes at 140o C describes in detail as table 5).The exemplary plot 1300(that Figure 13 has shown glucose yield per-cent 1302 and the relation of recovered frequency 1304 of with 1% acid solution, sample being processed to 10 minutes at 150oC describes in detail as table 5).As shown in the figure, under 120oC condition, glucose yield increases with each recovered frequency.But under 140oC condition and 150oC condition, glucose yield changes with continuous recovery.
The analytical results of the relation of acetic acid and recovered frequency has been shown in Figure 14-16.Especially, the exemplary plot 1400(that Figure 14 has shown yield of acetic acid per-cent 1402 and the relation of recovered frequency 1404 of with various acid solutions, sample being processed to 120 minutes at 120oC describes in detail as table 5).The exemplary plot 1500(that Figure 15 has shown yield of acetic acid per-cent 1502 and the relation of recovered frequency 1504 of with various acid solutions, sample being processed to 20 minutes at 140oC describes in detail as table 5).The exemplary plot 1600(that Figure 16 has shown yield of acetic acid per-cent 1602 and the relation of recovered frequency 1604 of with 1% acid solution, sample being processed 10 minutes and processed at 130oC 60 minutes at 150oC describes in detail as table 5).As shown in the figure, acetic acid concentration increases with each recovered frequency.In continuous circulation, yield of acetic acid keeps consistent (per-cent) relatively.Higher acid concentration trends towards causing higher acetic acid to form, and this may depend on the severe degree of processing.
The analytical results of the relation of furfural and recovered frequency has been shown in Figure 17-19.Especially, the exemplary plot 1700(that Figure 17 has shown furfural content 1702 and the relation of recovered frequency 1704 of with various acid solutions, sample being processed to 120 minutes at 120oC describes in detail as table 5).The exemplary plot 1800(that Figure 18 has shown furfural content per-cent 1802 and the relation of recovered frequency 1804 of with various acid solutions, sample being processed to 20 minutes at 140oC describes in detail as table 5).The exemplary plot 1900(that Figure 19 has shown furfural content 1902 and the relation of recovered frequency 1904 of with 1% acid solution, sample being processed 10 minutes and processed at 130oC 60 minutes at 150oC describes in detail as table 5).As shown in the figure, under all conditions, acetic acid concentration increases with each recovered frequency.Further, the furfural level of 1.6% sour loading capacity is high more a lot of than the furfural level of 1% sour loading capacity.Under 1% acid the reduction of output and under 1.6% acid the increase of output be tending towards showing the recovery along with xylose solution for 1% acid, pretreated severe degree reduces, and for 1.6% acid, pretreated severe degree increases.This may be the result improving owing to producing higher acetic acid and acid catalysis level.
Table 6 has been summed up experimental data with tabulated form.1% acid, 120oC, 2 hours xylose solutions reclaim pre-treatment and cause the wood sugar output of 85-100% and the glucose yield of 45-55% (from low enzyme dosage).In the time utilizing 1.2% sulfuric acid, produce the highest wood sugar output.By contrast, 1% acid produces the highest glucose level.Wood sugar output between 90 and 100% is to utilize 1.6% sour loading capacity to realize.Than wood sugar output, the acid with 1% is carried out pre-treatment and is produced the yield of acetic acid of about 80-85% and carry out pre-treatment with 1.6% acid and produce the yield of acetic acid of 85-95% and shown identical trend.Be created in the ascendant trend that glucose yield between 45% and 65% has been shown about 55-65% in 5 pre-treatment circulations by 1.6% sour loading capacity, and in fact 1% acid seem to cause glucose yield to reduce with its recovery.
The xylose solution of 150oC reclaim pretreated wood sugar output approach 100% and glucose yield start to approach 60% but then decline, reach stable state in 50% scope, pre-treatment also produces the available acetic acid of theory of about 85-90%.
130 ° of pretreated wood sugar output of C, in the scope of 90-95%, have shown that yield reducation, also can see same trend at yield of acetic acid with the development of reclaiming.Temperature rises to 150 ° of C from 130 ° of C and causes wood sugar to be converted into the amount increase of furfural.Sugar, acetic acid, and these trend supports of furfural production be evaluated at identical sour water flat under, to the longer time period (10 minutes compared with 60 minutes), 150 ° of C provide higher pretreated severe degree than 130 ° of C.
When check the trend of wood sugar output in whole experimental design time, the recovery of 1% acid has a declining tendency, and this shows not reclaim enough acid and xylose solution to keep violent level.On the contrary, 1.6% sour data presentation xylose and glucose output increases, and this shows that severe degree increases, and causes the pre-treatment of higher output yield, and this may be because acetic acid level improves.For 1.2% and 1.4% acid, xylose and glucose acid yield keeps relative stability.
* * *
The embodiment (comprising drawings and Examples) of disclosure and description of the present invention is intended to the present invention to carry out illustration and explanation.Based on the embodiment disclosed herein, for example, to (maybe will adopt) equipment and process used, and composition and treatment process, can modify and change; All these type of modifications and variations are all interpreted as being contained in scope of the present invention.
Word " demonstration " or " example " are intended to represent example, give an example or illustration.Any embodiment or design are described to " demonstration ", and do not mean that its relative other embodiment or design are that must recommend or preferred, do not mean that demonstration structure and the technology that the those of ordinary skill in this field is equal to got rid of yet.In contrast, the use of word " demonstration ", be intended to give specific form to concept, and subject content of the present invention is not limited to this type of example.
Word " or " be intended to expression " comprising " but not " only limiting to ".In this meaning, " comprise ", " having ", " containing " and other details describe or claim in similar word used, for avoiding ambiguity, this type of word is all intended to represent " comprising ", similar to " comprising ", use as open switching word, but not get rid of any additional or other element.
Claims (16)
1. for a method for preprocessing lignocellulose biomass, comprising:
A) acid solution is applied to first part's biomass;
B) described first part biomass are remained on to the temperature of rising, thereby obtain the approximately more than 80% wood sugar output of theoretical wood sugar output, wherein, in keeping the temperature of this rising, make liquid xylose solution and dextran solid from described first part biomass;
C) liquid at least a portion xylose solution is separated with dextran solid;
D) described operative liquid xylose solution is applied to further part biomass;
E) supplementary acid solution is applied to described further part biomass;
F) described further part biomass are remained on to the temperature of rising, thereby obtain the approximately more than 80% wood sugar output of theoretical wood sugar output, wherein, in keeping the temperature of this rising, make liquid xylose solution and dextran solid from described further part biomass; And
G) repeating step is c) to f).
2. method according to claim 1, is characterized in that, further comprises and discharges sugared glucose.
3. method according to claim 2, is characterized in that, in approximately more than 45% glucose yield of step b) and step f) acquisition glucose theoretical yield.
4. method according to claim 2, is characterized in that, in approximately more than 50% glucose yield of step b) and step f) acquisition glucose theoretical yield.
5. method according to claim 1, is characterized in that, described in remain on rising temperature comprise and maintain the temperature at about 120o C and 150o C.
6. method according to claim 1, is characterized in that, described in remain on rising temperature comprise that the temperature that remains on rising was at least about 10 minutes.
7. method according to claim 1, is characterized in that, described in remain on rising temperature comprise that the temperature that remains on rising is less than approximately 120 minutes.
8. method according to claim 1, is characterized in that, application acid solution comprises the sulfuric acid of application approximately 1% ~ 1.6%.
9. method according to claim 1, is characterized in that, described biomass comprise ground corn cob.
10. method according to claim 1, is characterized in that, described biomass comprise ground corn cob and maize straw.
11. methods according to claim 1, is characterized in that, obtain the approximately more than 90% wood sugar output of theoretical wood sugar output in step b) and step f).
12. methods according to claim 1, is characterized in that, described liquid xylose solution comprises the furfural lower than approximately 4000 ppm.
13. methods according to claim 1, is characterized in that, described liquid xylose solution comprises the furfural lower than approximately 3000 ppm.
14. methods according to claim 1, is characterized in that, described operative liquid xylose solution accounts for approximately 70% of total xylose solution.
15. methods according to claim 1, is characterized in that, described operative liquid xylose solution accounts for approximately 75% of total xylose solution.
16. 1 kinds of methods for preprocessing lignocellulose biomass, described lignocellulose biomass will be supplied to fermentation system to produce tunning, and described method comprises:
A) xylose solution is applied to biomass;
B) supplemental acid solution is applied to described biomass;
C) described biomass are remained on to the temperature of rising, thereby obtain the approximately more than 80% wood sugar output of theoretical wood sugar output, wherein, in keeping the temperature of this rising, make xylose solution and dextran solid from described biomass;
D) at least a portion xylose solution is separated with described dextran solid;
E) repeating step is a) to d).
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US201161505389P | 2011-07-07 | 2011-07-07 | |
| US61/505,389 | 2011-07-07 | ||
| PCT/US2012/045953 WO2013006856A1 (en) | 2011-07-07 | 2012-07-09 | Systems and methods for acid recycle |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103842524A true CN103842524A (en) | 2014-06-04 |
Family
ID=47437487
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201280033775.8A Pending CN103842524A (en) | 2011-07-07 | 2012-07-09 | Systems and methods for acid recycle |
Country Status (7)
| Country | Link |
|---|---|
| US (2) | US9982317B2 (en) |
| EP (1) | EP2729585A4 (en) |
| CN (1) | CN103842524A (en) |
| BR (1) | BR112014000351A2 (en) |
| CA (1) | CA2840995A1 (en) |
| MX (1) | MX2014000245A (en) |
| WO (1) | WO2013006856A1 (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9068206B1 (en) | 2009-03-03 | 2015-06-30 | Poet Research, Inc. | System for treatment of biomass to facilitate the production of ethanol |
| US10533203B2 (en) | 2010-03-19 | 2020-01-14 | Poet Research, Inc. | System for the treatment of biomass |
| US9034620B2 (en) | 2010-03-19 | 2015-05-19 | Poet Research, Inc. | System for the treatment of biomass to facilitate the production of ethanol |
| US9469859B1 (en) | 2010-08-12 | 2016-10-18 | Poet Research, Inc. | Method for treatment of biomass |
| WO2012099967A1 (en) | 2011-01-18 | 2012-07-26 | Poet, Llc | Systems and methods for hydrolysis of biomass |
| US9278379B2 (en) | 2012-06-15 | 2016-03-08 | Poet Research, Inc. | Methods and systems for reducing the level of one or more impurities that are present in a pretreated cellulosic material and/or distillate |
| US9611493B2 (en) | 2013-08-01 | 2017-04-04 | Renmatix, Inc. | Method for biomass hydrolysis |
| US9738729B2 (en) * | 2014-02-19 | 2017-08-22 | Api Intellectual Property Holdings, Llc | Processes and apparatus for removal of fermentation inhibitors from biomass hydrolysates |
| WO2016183336A1 (en) | 2015-05-13 | 2016-11-17 | Poet Research, Inc. | Methods of reducing the size of lignocellulosic material, and related systems |
| US10618850B2 (en) | 2015-10-15 | 2020-04-14 | Poet Research, Inc. | Methods of extracting inorganic nutrients from pretreated biomass to form a fertilizer composition, and related systems |
| CA3215759A1 (en) | 2015-11-24 | 2017-06-01 | Poet Research, Inc. | Using dissolved oxygen to inhibit lactic acid production during propagation of yeast and/or hydrolysis of lignocellulosic biomass |
| EP3383971A1 (en) * | 2015-12-04 | 2018-10-10 | Arbiom SAS | System and method for treatment of biomass for the production of biofuels and biochemicals |
| US20170191099A1 (en) * | 2015-12-04 | 2017-07-06 | Arbiom Inc. | System and method for treatment of biomass for the production of biofuels and biochemicals |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2734836A (en) * | 1956-02-14 | Production of pentoses from cellulosic materials | ||
| US4072538A (en) * | 1975-10-08 | 1978-02-07 | Sud-Chemie Ag | Process for the two-stage decomposition of hemi-celluloses to xylose |
| DD222636A1 (en) * | 1984-04-05 | 1985-05-22 | Inst Forstwissenschaften | METHOD FOR OBTAINING XYL-RELATED HYDROLYSATES WITH INCREASED SUGAR CONCENTRATION FROM HEMICELLULOSE-CONTAINING RAW MATERIALS |
| WO1992007098A1 (en) * | 1990-10-23 | 1992-04-30 | Agrocinq Recherche S.A. | Process and plant for preparing pentose and/or hexose concentrated juice from hemicellulose-rich plant substances |
| US5188673A (en) * | 1987-05-15 | 1993-02-23 | Clausen Edgar C | Concentrated sulfuric acid process for converting lignocellulosic materials to sugars |
| US5424417A (en) * | 1993-09-24 | 1995-06-13 | Midwest Research Institute | Prehydrolysis of lignocellulose |
| US6512110B1 (en) * | 1997-06-10 | 2003-01-28 | Xyrofin Oy | Process for the production of xylose from a paper-grade hardwood pulp |
| US20080026431A1 (en) * | 2006-07-19 | 2008-01-31 | Taisei Corporation | Method for saccharification of woody biomass |
| US20110065159A1 (en) * | 2009-07-01 | 2011-03-17 | Raines Ronald T | Biomass hydrolysis |
Family Cites Families (137)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE222636C (en) | ||||
| US3212932A (en) | 1963-04-12 | 1965-10-19 | Georgia Pacific Corp | Selective hydrolysis of lignocellulose materials |
| US4014743A (en) | 1973-01-10 | 1977-03-29 | Penick & Ford, Limited | Method for continuous preparation of cooked thinned starch pastes |
| US4152197A (en) | 1974-09-23 | 1979-05-01 | Mo Och Domsjo Ab | Process for preparing high-yield cellulose pulps by vapor phase pulping an unpulped portion of lignocellulosic material and a partially chemically pulped portion |
| FI51371C (en) | 1974-10-04 | 1976-12-10 | Rosenlew Ab Oy W | Method for decomposing a polysaccharide-containing raw material by acid hydrolysis. |
| GB1548500A (en) | 1977-05-17 | 1979-07-18 | Inst Voor Bewaring | Process for obtaining xylose by hydrolysis of residues of annuals |
| CA1096374A (en) | 1977-07-11 | 1981-02-24 | Edward A. Delong | Method of rendering lignin separable from cellulose and hemicellulose in lignocellulosic material and the product so produced |
| US5221357A (en) | 1979-03-23 | 1993-06-22 | Univ California | Method of treating biomass material |
| US5366558A (en) | 1979-03-23 | 1994-11-22 | Brink David L | Method of treating biomass material |
| US5628830A (en) | 1979-03-23 | 1997-05-13 | The Regents Of The University Of California | Enzymatic hydrolysis of biomass material |
| US4342831A (en) | 1979-07-02 | 1982-08-03 | American Can Company | Fermentable acid hydrolyzates and fermentation process |
| US4425433A (en) | 1979-10-23 | 1984-01-10 | Neves Alan M | Alcohol manufacturing process |
| FI58346C (en) | 1979-12-18 | 1981-01-12 | Tampella Oy Ab | FOERFARANDE FOER KONTINUERLIG FOERSOCKRING AV CELLULOSA AV VAEXTMATERIAL |
| CA1173380A (en) | 1980-02-19 | 1984-08-28 | Michael I. Sherman | Acid hydrolysis of biomass for ethanol production |
| ES499625A0 (en) | 1980-02-23 | 1981-12-16 | Reitter Franz Johann | PROCEDURE AND INSTALLATION FOR THE CONTINUOUS HYDROLYSIS OF HEMICELLULOSE CONTAINING PENTOSANES OF CELLULOSE. |
| US4461648A (en) | 1980-07-11 | 1984-07-24 | Patrick Foody | Method for increasing the accessibility of cellulose in lignocellulosic materials, particularly hardwoods agricultural residues and the like |
| BR8102802A (en) | 1981-04-30 | 1982-12-14 | Villares Ind | PROCESS AND INSTALLATION TO OBTAIN ETHANOL BY CONTINUOUS ACID HYDROLYSIS OF CELLULOSIC MATERIALS |
| DE3379063D1 (en) | 1982-07-05 | 1989-03-02 | Erne Fittings Gmbh & Co | Process and apparatus for the preparation of cellulose, simple sugars and soluble lignine from vegetable biomasse |
| US4552616A (en) | 1982-10-20 | 1985-11-12 | New Fibers International Inc. | Pulping process pretreatment using a lower alkanolamine in the presence of ammonium hydroxide |
| GB8406866D0 (en) | 1984-03-16 | 1984-04-18 | British Petroleum Co Plc | Separating cellulose and hemicellulose |
| US4668340A (en) | 1984-03-20 | 1987-05-26 | Kamyr, Inc. | Method of countercurrent acid hydrolysis of comminuted cellulosic fibrous material |
| CA1225636A (en) | 1984-07-13 | 1987-08-18 | Robert P. Chang | Method for continuous countercurrent organosolv saccharification of wood and other lignocellulosic materials |
| US4752579A (en) | 1985-10-21 | 1988-06-21 | Uop Inc. | Monosaccharides from corn kernel hulls by hydrolysis |
| CA1275286C (en) | 1986-05-29 | 1990-10-16 | Edward A. Delong | Method for extracting the chemical components from dissociated lignocellulosic material |
| FR2609046B1 (en) | 1986-12-30 | 1989-07-13 | Bourgogne Biodyne | PROCESS FOR THE CONTINUOUS PRODUCTION OF ETHANOL BY COLD HYDROLYSIS AND SIMULTANEOUS FERMENTATION OF A BROKEN AMYLACE SUBSTRATE |
| US4997488A (en) | 1988-02-05 | 1991-03-05 | The United States Of America As Represented By The Secretary Of Agriculture | Combined physical and chemical treatment to improve lignocellulose digestibility |
| NZ229080A (en) | 1989-05-11 | 1991-10-25 | Convertech Group Ltd | Two stage process and equipment for the steam hydrolysis of woody material |
| FI85384C (en) | 1989-09-06 | 1992-04-10 | Cultor Oy | Process for hydrolyzing hemicellulose with immobilized enzymes and product comprising an immobilized hemicellulolytic enzyme |
| US5171592A (en) | 1990-03-02 | 1992-12-15 | Afex Corporation | Biomass refining process |
| US5125977A (en) * | 1991-04-08 | 1992-06-30 | The United States Of America As Represented By The United States Department Of Energy | Two-stage dilute acid prehydrolysis of biomass |
| US5411594A (en) * | 1991-07-08 | 1995-05-02 | Brelsford; Donald L. | Bei hydrolysis process system an improved process for the continuous hydrolysis saccharification of ligno-cellulosics in a two-stage plug-flow-reactor system |
| US5865898A (en) | 1992-08-06 | 1999-02-02 | The Texas A&M University System | Methods of biomass pretreatment |
| US5693296A (en) | 1992-08-06 | 1997-12-02 | The Texas A&M University System | Calcium hydroxide pretreatment of biomass |
| WO1994008027A1 (en) | 1992-09-28 | 1994-04-14 | Midwest Research Institute | Fermentation of cellulose and hemicellulose in corn fiber and distillers dried grains with solubles to ethanol |
| US5370999A (en) | 1992-12-17 | 1994-12-06 | Colorado State University Research Foundation | Treatment of fibrous lignocellulosic biomass by high shear forces in a turbulent couette flow to make the biomass more susceptible to hydrolysis |
| US5338366A (en) | 1993-01-04 | 1994-08-16 | Kamyr, Inc. | Acid pre-hydrolysis reactor system |
| US5597714A (en) | 1993-03-26 | 1997-01-28 | Arkenol, Inc. | Strong acid hydrolysis of cellulosic and hemicellulosic materials |
| US5562777A (en) | 1993-03-26 | 1996-10-08 | Arkenol, Inc. | Method of producing sugars using strong acid hydrolysis of cellulosic and hemicellulosic materials |
| US5782982A (en) | 1993-03-26 | 1998-07-21 | Arkenol, Inc. | Method of removing silica or silicates from solids resulting from the strong acid hydrolysis of cellulosic and hemicellulosic materials |
| WO1994029475A1 (en) | 1993-06-11 | 1994-12-22 | Midwest Research Institute | Cell mass from fermenters as nutrient source in biomass-to-ethanol conversion |
| US5571703A (en) | 1993-12-23 | 1996-11-05 | Controlled Environmental Systems Corporation | Municipal solid waste processing facility and commercial ethanol production process |
| US5705369A (en) | 1994-12-27 | 1998-01-06 | Midwest Research Institute | Prehydrolysis of lignocellulose |
| US5932456A (en) | 1995-06-07 | 1999-08-03 | Ingram-Howell, L.L.C. | Production of ethanol and other fermentation products from biomass |
| US6325888B1 (en) | 1995-08-31 | 2001-12-04 | Andritz-Ahlstrom Inc. | Method for pulping sawdust |
| US5972118A (en) | 1995-10-27 | 1999-10-26 | Tennessee Valley Authority | Concentrated sulfuric acid hydrolysis of lignocellulosics |
| BR9600672A (en) | 1996-03-08 | 1997-12-30 | Dedini S A Administracao E Par | Acid hydrolysis process of lignocellulosic material and hydrolysis reactor |
| US5711817A (en) | 1996-05-01 | 1998-01-27 | Eau-Viron Incorporated | Method for the continuous conversion of cellulosic material to sugar |
| US6022419A (en) * | 1996-09-30 | 2000-02-08 | Midwest Research Institute | Hydrolysis and fractionation of lignocellulosic biomass |
| US6228177B1 (en) | 1996-09-30 | 2001-05-08 | Midwest Research Institute | Aqueous fractionation of biomass based on novel carbohydrate hydrolysis kinetics |
| US7883872B2 (en) | 1996-10-10 | 2011-02-08 | Dyadic International (Usa), Inc. | Construction of highly efficient cellulase compositions for enzymatic hydrolysis of cellulose |
| US5733758A (en) | 1997-01-10 | 1998-03-31 | Nguyen; Quang A. | Tower reactors for bioconversion of lignocellulosic material |
| US5769934A (en) | 1997-01-15 | 1998-06-23 | Fmc Corporation | Method for producing microcrystalline cellulose |
| US5916780A (en) | 1997-06-09 | 1999-06-29 | Iogen Corporation | Pretreatment process for conversion of cellulose to fuel ethanol |
| PT887024E (en) | 1997-06-23 | 2004-10-29 | Nestle Sa | NUTRITIVE COMPOSITION UNDERSTANDING PEAR AND INULIN FIBERS |
| US5968362A (en) | 1997-08-04 | 1999-10-19 | Controlled Enviromental Systems Corporation | Method for the separation of acid from sugars |
| WO2000014120A1 (en) | 1998-09-09 | 2000-03-16 | Forskningscenter Risø | A process for solubilizing hemicellulose present in a lignocellulosic material |
| US6007636A (en) | 1999-01-04 | 1999-12-28 | Lightner; Gene E. | Method to recycle an aqueous acidic liquor used for depolymerization of cellulose |
| EP1161592B1 (en) | 1999-02-15 | 2004-09-22 | Kiram AB | Process for oxygen pulping of lignocellulosic material and recovery of pulping chemicals |
| DE19916347C1 (en) | 1999-04-12 | 2000-11-09 | Rhodia Acetow Ag | Process for separating biomass containing lignocellulose |
| NO310717B1 (en) | 1999-05-31 | 2001-08-20 | Cambi As | Process and apparatus for continuous hydrolysis of wastewater |
| BR9902607B1 (en) | 1999-06-23 | 2010-08-24 | biomass pre-hydrolysis apparatus and process. | |
| CA2318027C (en) | 1999-09-13 | 2008-07-08 | Andritz-Ahlstrom Inc. | Treating pulp with yield or strength-enhancing additive |
| WO2001032715A1 (en) | 1999-11-02 | 2001-05-10 | Waste Energy Integrated Sytems, Llc | Process for the production of organic products from lignocellulose containing biomass sources |
| ATE411971T1 (en) | 2000-02-17 | 2008-11-15 | Univ Denmark Tech Dtu | METHOD FOR TREATING MATERIALS CONTAINING LIGNIN AND CELLULOSE |
| ES2166316B1 (en) | 2000-02-24 | 2003-02-16 | Ct Investig Energeticas Ciemat | PROCEDURE FOR THE PRODUCTION OF ETHANOL FROM LIGNOCELLULOSIC BIOMASS USING A NEW THERMOTOLERING YEAST. |
| US6423145B1 (en) * | 2000-08-09 | 2002-07-23 | Midwest Research Institute | Dilute acid/metal salt hydrolysis of lignocellulosics |
| US6419788B1 (en) | 2000-08-16 | 2002-07-16 | Purevision Technology, Inc. | Method of treating lignocellulosic biomass to produce cellulose |
| EP1320588B2 (en) | 2000-09-25 | 2017-06-28 | Iogen Energy Corporation | Method for glucose production with a cellulase mixture comprising a modified cellulase |
| AU2002210409A1 (en) | 2000-11-10 | 2002-05-21 | Novozymes A/S | Ethanol process |
| BR0007374A (en) | 2000-12-08 | 2002-08-20 | Pre-hydrolysis system for waste organic matter and waste industrialization process | |
| US6692578B2 (en) | 2001-02-23 | 2004-02-17 | Battelle Memorial Institute | Hydrolysis of biomass material |
| EP2261381A3 (en) | 2001-02-28 | 2012-05-30 | Iogen Energy Corporation | Method of Processing Lignocellulosic Feedstock for Enhanced Xylose and Ethanol Production |
| WO2003013714A1 (en) | 2001-08-11 | 2003-02-20 | Sicco K/S | Method for transfer of particulate solid products between zones of different pressure. |
| US7189306B2 (en) | 2002-02-22 | 2007-03-13 | Gervais Gibson W | Process of treating lignocellulosic material to produce bio-ethanol |
| CA2479248C (en) | 2002-03-15 | 2011-09-27 | Iogen Energy Corporation | Method for glucose production using endoglucanase core protein for improved recovery and reuse of enzyme |
| WO2004005608A1 (en) | 2002-07-02 | 2004-01-15 | Andritz, Inc. | Solvent pulping of biomass |
| GB0218019D0 (en) | 2002-08-05 | 2002-09-11 | Ciba Spec Chem Water Treat Ltd | Production of a fermentation product |
| US7604967B2 (en) | 2003-03-19 | 2009-10-20 | The Trustees Of Dartmouth College | Lignin-blocking treatment of biomass and uses thereof |
| WO2005067531A2 (en) | 2004-01-16 | 2005-07-28 | Novozymes Inc. | Methods for degrading lignocellulosic materials |
| BRPI0509886B1 (en) | 2004-04-13 | 2018-01-30 | Iogen Energy Corporation | Method for processing a lignocellulosic raw material and obtaining an inorganic salt |
| FI118012B (en) | 2004-06-04 | 2007-05-31 | Valtion Teknillinen | Process for producing ethanol |
| AU2005282168C1 (en) | 2004-09-10 | 2011-03-17 | Iogen Energy Corporation | Process for producing a pretreated feedstock |
| DK176540B1 (en) | 2004-09-24 | 2008-07-21 | Cambi Bioethanol Aps | Process for the treatment of biomass and organic waste in order to extract desired biologically based products |
| US7198925B2 (en) | 2004-09-30 | 2007-04-03 | Iogen Energy Corporation | Pre-treatment of bales of feedstock |
| JP2008514207A (en) | 2004-09-30 | 2008-05-08 | アイオゲン エナジー コーポレイション | Continuous flow pretreatment system with steam recovery |
| CN101090962B (en) | 2004-11-29 | 2012-04-18 | 因必康有限公司 | Enzymatic hydrolysis of biomasses having a high dry matter (DM) content |
| US7503981B2 (en) | 2004-12-02 | 2009-03-17 | The Trustees Of Dartmouth College | Removal of minerals from cellulosic biomass |
| EP1690980A1 (en) | 2005-02-11 | 2006-08-16 | Agrotechnology and Food Innovations B.V. | Process and apparatus for conversion of biomass |
| BRPI0500534A (en) | 2005-02-15 | 2006-10-10 | Oxiteno Sa Ind E Comercio | acid hydrolysis process of cellulosic and lignocellulosic materials, digestion vessel and hydrolysis reactor |
| WO2006113683A2 (en) | 2005-04-19 | 2006-10-26 | Archer-Daniels-Midland Company | Process for the production of animal feed and ethanol and novel feed |
| EP1885864A4 (en) | 2005-06-03 | 2011-04-13 | Iogen Energy Corp | Method of continuous processing of lignocellulosic feedstocks |
| US8980598B2 (en) | 2005-06-14 | 2015-03-17 | Danisco Us Inc. | Dry solids staging fermentation process |
| RU2432368C2 (en) | 2005-07-19 | 2011-10-27 | Инбикон А/С | Method of converting cellulose material to ethanol |
| CA2651628C (en) | 2006-05-08 | 2015-01-06 | Biojoule Ltd. | Process for the production of biofuel from plant materials |
| EP2069406A4 (en) | 2006-09-01 | 2012-03-28 | Ra Energy Corp | Advanced biorefinery process |
| US7666637B2 (en) | 2006-09-05 | 2010-02-23 | Xuan Nghinh Nguyen | Integrated process for separation of lignocellulosic components to fermentable sugars for production of ethanol and chemicals |
| WO2008048513A2 (en) | 2006-10-13 | 2008-04-24 | Rowan University | Ethanol resistant and furfural resistant strains of e. coli fbr5 for production of ethanol from cellulosic biomass |
| US7670813B2 (en) | 2006-10-25 | 2010-03-02 | Iogen Energy Corporation | Inorganic salt recovery during processing of lignocellulosic feedstocks |
| US7815741B2 (en) | 2006-11-03 | 2010-10-19 | Olson David A | Reactor pump for catalyzed hydrolytic splitting of cellulose |
| US7815876B2 (en) | 2006-11-03 | 2010-10-19 | Olson David A | Reactor pump for catalyzed hydrolytic splitting of cellulose |
| US20100143974A1 (en) | 2007-02-01 | 2010-06-10 | Chang-Ho Chung | Process for Sugar Production from Lignocellulosic Biomass Using Alkali Pretreatment |
| US20080184709A1 (en) | 2007-02-07 | 2008-08-07 | Rowell Dean W | Turbine power generation using lignin-based fuel |
| WO2008131229A1 (en) | 2007-04-19 | 2008-10-30 | Mascoma Corporation | Combined thermochemical pretreatment and refining of lignocellulosic biomass |
| US20080277082A1 (en) | 2007-05-07 | 2008-11-13 | Andritz Inc. | High pressure compressor and steam explosion pulping method |
| US9260818B2 (en) | 2007-05-23 | 2016-02-16 | Andritz Inc. | Single vessel reactor system for hydrolysis and digestion of wood chips with chemical enhanced wash method |
| US7807419B2 (en) | 2007-08-22 | 2010-10-05 | E. I. Du Pont De Nemours And Company | Process for concentrated biomass saccharification |
| US7819976B2 (en) | 2007-08-22 | 2010-10-26 | E. I. Du Pont De Nemours And Company | Biomass treatment method |
| EP2592151A3 (en) | 2007-12-21 | 2014-07-30 | Inbicon A/S | Non-sterile fermentation of bioethanol |
| FR2926824A1 (en) | 2008-01-25 | 2009-07-31 | Cie Ind De La Matiere Vegetale | PROCESS FOR PRETREATMENT OF LIGNOCELLULOSIC PLANT MATERIAL FOR PRODUCTION OF BIOETHANOL |
| US8057639B2 (en) | 2008-02-28 | 2011-11-15 | Andritz Inc. | System and method for preextraction of hemicellulose through using a continuous prehydrolysis and steam explosion pretreatment process |
| US20090308383A1 (en) | 2008-06-10 | 2009-12-17 | Andritz Inc. | Apparatus and method for hydrolysis of cellulosic material in a multi-step process to produce c5 and c6 sugars using a single vessel |
| US8529765B2 (en) | 2008-12-09 | 2013-09-10 | Sweetwater Energy, Inc. | Ensiling biomass for biofuels production and multiple phase apparatus for hydrolyzation of ensiled biomass |
| CN102307485B (en) | 2008-12-23 | 2013-11-06 | 波伊特研究股份有限公司 | System for production of ethanol and co-products |
| US20100233771A1 (en) | 2009-03-03 | 2010-09-16 | Mcdonald William F | System for pre-treatment of biomass for the production of ethanol |
| EP2403954B1 (en) | 2009-03-03 | 2015-04-22 | POET Research, Inc. | Method for fermentation of biomass for the production of ethanol |
| US9068206B1 (en) | 2009-03-03 | 2015-06-30 | Poet Research, Inc. | System for treatment of biomass to facilitate the production of ethanol |
| TW201040279A (en) | 2009-03-31 | 2010-11-16 | Chemtex Italia S R L | Improved biomass pretreatment process |
| AR075995A1 (en) | 2009-03-31 | 2011-05-11 | Chemtex Italia S R L | A PROCESS FOR HYDROLYSIS OF BIOMASS WITH HIGH CONTENT OF SOLIDS |
| US20160369304A9 (en) | 2009-05-18 | 2016-12-22 | Poet Research, Inc. | System for treatment of biomass to facilitate the production of ethanol |
| US20120137572A1 (en) | 2009-05-22 | 2012-06-07 | Kior, Inc. | Processing biomass with a hydrogen source |
| US8852301B1 (en) | 2009-06-30 | 2014-10-07 | Poet Research, Inc. | Composition of lignin pellets and system for producing |
| US8597431B2 (en) | 2009-10-05 | 2013-12-03 | Andritz (Usa) Inc. | Biomass pretreatment |
| CA2769746C (en) * | 2010-01-19 | 2013-10-15 | Renmatix, Inc. | Production of fermentable sugars and lignin from biomass using supercritical fluids |
| US9034620B2 (en) | 2010-03-19 | 2015-05-19 | Poet Research, Inc. | System for the treatment of biomass to facilitate the production of ethanol |
| US10533203B2 (en) | 2010-03-19 | 2020-01-14 | Poet Research, Inc. | System for the treatment of biomass |
| WO2011159915A1 (en) | 2010-06-17 | 2011-12-22 | Poet Research, Inc. | Fermentation of biomass |
| US8057641B2 (en) | 2010-07-19 | 2011-11-15 | Kior Inc. | Method and apparatus for pyrolysis of a biomass |
| IT1402200B1 (en) | 2010-09-29 | 2013-08-28 | Chemtex Italia S R L Ora Chemtex Italia S P A | IMPROVED PROCEDURE TO RECOVER SUGAR FROM A LIGNOCELLULOSIC BIOMASS PRETREATMENT FLOW |
| IT1402202B1 (en) | 2010-09-29 | 2013-08-28 | Chemtex Italia S R L Ora Chemtex Italia S P A | IMPROVED PROCEDURE TO RECOVER SUGAR FROM A LIGNOCELLULOSIC BIOMASS PRETREATMENT FLOW |
| US9187862B2 (en) * | 2010-11-05 | 2015-11-17 | Greenfield Specialty Alcohols Inc. | Bagasse fractionation for cellulosic ethanol and chemical production |
| PT106039A (en) * | 2010-12-09 | 2012-10-26 | Hcl Cleantech Ltd | PROCESSES AND SYSTEMS FOR PROCESSING LENHOCELLULOSIC MATERIALS AND RELATED COMPOSITIONS |
| WO2012099967A1 (en) | 2011-01-18 | 2012-07-26 | Poet, Llc | Systems and methods for hydrolysis of biomass |
| WO2012100187A1 (en) | 2011-01-21 | 2012-07-26 | Poet Research, Inc. | Systems and methods for improving fermentation |
| WO2012103281A2 (en) | 2011-01-27 | 2012-08-02 | Poet Research, Inc. | Systems and methods for mitigation of inhibitors using yeast |
| EP2694723A1 (en) | 2011-04-01 | 2014-02-12 | University of Limerick | Lignocellulose processing |
| CN103635582A (en) * | 2011-06-10 | 2014-03-12 | 先正达参股股份有限公司 | Methods for treating lignocellulosic material |
| US9278379B2 (en) | 2012-06-15 | 2016-03-08 | Poet Research, Inc. | Methods and systems for reducing the level of one or more impurities that are present in a pretreated cellulosic material and/or distillate |
-
2012
- 2012-07-09 US US14/130,878 patent/US9982317B2/en active Active
- 2012-07-09 BR BR112014000351A patent/BR112014000351A2/en not_active Application Discontinuation
- 2012-07-09 WO PCT/US2012/045953 patent/WO2013006856A1/en active Application Filing
- 2012-07-09 CA CA2840995A patent/CA2840995A1/en not_active Abandoned
- 2012-07-09 MX MX2014000245A patent/MX2014000245A/en unknown
- 2012-07-09 EP EP12807051.3A patent/EP2729585A4/en not_active Withdrawn
- 2012-07-09 CN CN201280033775.8A patent/CN103842524A/en active Pending
-
2018
- 2018-04-20 US US15/958,895 patent/US10731229B2/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2734836A (en) * | 1956-02-14 | Production of pentoses from cellulosic materials | ||
| US4072538A (en) * | 1975-10-08 | 1978-02-07 | Sud-Chemie Ag | Process for the two-stage decomposition of hemi-celluloses to xylose |
| DD222636A1 (en) * | 1984-04-05 | 1985-05-22 | Inst Forstwissenschaften | METHOD FOR OBTAINING XYL-RELATED HYDROLYSATES WITH INCREASED SUGAR CONCENTRATION FROM HEMICELLULOSE-CONTAINING RAW MATERIALS |
| US5188673A (en) * | 1987-05-15 | 1993-02-23 | Clausen Edgar C | Concentrated sulfuric acid process for converting lignocellulosic materials to sugars |
| WO1992007098A1 (en) * | 1990-10-23 | 1992-04-30 | Agrocinq Recherche S.A. | Process and plant for preparing pentose and/or hexose concentrated juice from hemicellulose-rich plant substances |
| US5424417A (en) * | 1993-09-24 | 1995-06-13 | Midwest Research Institute | Prehydrolysis of lignocellulose |
| US6512110B1 (en) * | 1997-06-10 | 2003-01-28 | Xyrofin Oy | Process for the production of xylose from a paper-grade hardwood pulp |
| US20080026431A1 (en) * | 2006-07-19 | 2008-01-31 | Taisei Corporation | Method for saccharification of woody biomass |
| US20110065159A1 (en) * | 2009-07-01 | 2011-03-17 | Raines Ronald T | Biomass hydrolysis |
Also Published As
| Publication number | Publication date |
|---|---|
| US20140209092A1 (en) | 2014-07-31 |
| US10731229B2 (en) | 2020-08-04 |
| WO2013006856A1 (en) | 2013-01-10 |
| CA2840995A1 (en) | 2013-01-10 |
| US9982317B2 (en) | 2018-05-29 |
| US20180237869A1 (en) | 2018-08-23 |
| EP2729585A4 (en) | 2015-03-18 |
| EP2729585A1 (en) | 2014-05-14 |
| MX2014000245A (en) | 2014-09-15 |
| BR112014000351A2 (en) | 2017-01-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103842524A (en) | Systems and methods for acid recycle | |
| US10738273B2 (en) | System for hydrolyzing a cellulosic feedstock slurry using one or more unmixed and mixed reactors | |
| Öhgren et al. | A comparison between simultaneous saccharification and fermentation and separate hydrolysis and fermentation using steam-pretreated corn stover | |
| CA2694875C (en) | Cellulase enzyme based method for the production of alcohol and glucose from pretreated lignocellulosic feedstock | |
| CA2824993C (en) | Systems and methods for hydrolysis of biomass | |
| Thomsen et al. | Preliminary results on optimization of pilot scale pretreatment of wheat straw used in coproduction of bioethanol and electricity | |
| CN101765663B (en) | Biomass pretreatment | |
| EP2547778B1 (en) | System for the treatment of biomass | |
| EP2336291B1 (en) | Apparatus for pretreating biomass using internal heat | |
| EA026271B1 (en) | Methods of processing lignocellulosic biomass using single-stage autohydrolysis and enzymatic hydrolysis with c5 bypass and post-hydrolysis | |
| WO2010011328A1 (en) | Hybrid process for the production of biofuel | |
| US20170362618A1 (en) | High solids enzymatic hydrolysis and fermentation of pretreated biomass | |
| EP3307898A1 (en) | Cellulosic biofuel and co-products | |
| US20220033860A1 (en) | Method for carring out the combined operation of a bioethanol production unit and a biogas unit | |
| US9611492B2 (en) | Use of vinasse in the process of saccharification of lignocellulosic biomass | |
| CN105400830A (en) | Method for producing ethyl alcohol through lignocellulose raw material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| AD01 | Patent right deemed abandoned | ||
| AD01 | Patent right deemed abandoned |
Effective date of abandoning: 20180313 |